Fungicidal composition with synergistic activity

ABSTRACT

There is described a fungicidal composition which comprises a synergistic amount of 
     (a) propyl 3-(dimethylamino)propylcarbamate or an acid addition salt thereof, and 
     (b) a compound selected from the group consisting of zinc propylenebis(dithiocarbamate) polymer (propineb), zinc ethylenebis(dithiocarbamate) polymer (zineb), manganese ethylenebis(dithiocarbamate) polymer (maneb), zinc ammoniate ethylenebis(dithiocarbamate)-poly(ethylenethiuramdisulphide) (metiram), tetrachloroisophthalonitrile (chlorothalonil) and copper(I)oxide, as well as carriers and/or other additives, 
     the ratio of component A to component B being preferably from about 1:0.1-3.

This invention relates to a fungicidal composition with synergisticactivity.

The composition contains, as essential ingredients, two components thatmutually affect each other when used together and display a biologicalactivity that is greater than the sum of the activities when used alone,an effect which is designated as synergism. This synergism leads to anincreased protective activity when treating plants against a largenumber of fungi.

Thus these fungicidal compositions can be used in plant protection forcombating Deuteromycetes, Zygomycetes, Basidiomycetes,Plasmodiophoraceae, Ascomycetes, Domycetes and Chytridiomycetes.

Compositions with fungicidal activity are already known and are thesubject of Patents such as for example DE OS No. 6 05 551. Mixtures offungicides that show a synergisitic activity are known (EP No. 106558and 40007). However, there is still a considerable need and in evengreater amounts for further compositions in this area with increasedactivity in order especially to meet the increased demands forprotection of the environment and to overcome resistance.

The object of the present invention is thus to provide a fungicidalcomposition with synergistic activity. This object is provided accordingto the invention, by a composition that is characterised by a content of

(a) propyl 3-(dimethylamino)propylcarbamate or an acid addition saltthereof, and

(b) a compound selected from the group consisting of zincpropylenebis(dithiocarbamate) polymer (propineb), zincethylenebis(dithiocarbamate) polymer (zineb). manganeseethylenebis(dithiocarbamate) polymer (maneb), zinc ammoniateethylenebis(dithiocarbamate) poly(ethylenethiuramdisulphide) (metiram),tetrachloro isophthalonitrile (chlorothalonil) and copper(I)oxide, aswell as carriers an other additives.

the ratio of component A to component B being preferably from about1:0.1-3.

Component A can be used in the form of an acid addition salt as well asits free base. The salts can be derived from inorganic or organic acids,such as mineral acids. mono or polycarboxylic acids or sulphonic acidsfor example: hydrochloric acid, sulphuric acid, formic acid, propionicacid, valeric acid, oxalic acid, malonic acid, succinic acid,cyanoacetic acid, chloroacetic acid, dichloroacetic acid,trifluoroacetic acid, benzoic acid, furan-2-carboxylic acid,p-toluenesulphonic acid, methanesulphonic acid, thioglycolic acid andcitric acid.

The compositions of the invention show a surprising fungicidal activitythat exceeds the sum of the activities of the individual components whenused alone. This synergistic activity could not be envisaged from thepresent state of knowledge.

The synergistic activity of the composition of the invention issignificantly displayed in a mixture ratio of 1 part by weight ofcomponent A to 0.1 to 3 parts by weight of component B, although theselimits can be exceeded by greater or smaller amounts by weight. Thecomposition of the invention shows increased activity in comparison tothe additive activity of the individual components if one part by weightof propamocarb (component A) is used in the mixture with:

0.5-1.5 parts by weight propineb

1.0-3.0 parts by weight zineb

0.5-1.5 parts by weight maneb

0.5-2.0 parts by weight metiram

0.5-2.0 parts by weight chlorothalonil

or 1.0-3.0 parts by weight copper(I)oxide

as component B.

However, the weight ratio of component A and B depends on thesensitivity and resistance of the plants, the time of application theclimatic conditions and the soil conditions.

The composition of the invention shows a wide fungicidal activityagainst fungi of various systematic types, such as: Aphanomyces; Bremia;Peronospora: Phytophthora; e.g. Phytophthora infestans;Pseudoperonospora, e.g. Pseudoperonospora humuli; Pythium and Plasmoparae.g. Plasmopara viticola.

In treating parts of the plant above the ground, protection is givenagainst wind-borne diseases. In order to protect against seed-bornediseases the compounds of the invention can be used as a seed treatment.Besides they also act systemically, that means they are taken up by theroots of the plant, for example after sowing, are transported into theparts of the plant above the earth and protect against these diseases

Because of the broad spectrum of activity that has been found, thecompositions are suitable not only for protection of crops, but also forprotection of materials and for combating microbes which are Pathogenicto humans and animals from which wide-ranging possibilities of usearise.

The rate of use lies as a rule from 500 to 9000 g of the mixture(components A and B)/ha, preferably 1700 to 3500 g mixture/ha.

The composition can be applied in conventional manner, for example withwater as carrier in spray amounts of about 100 to 2000 liters perhectare. Application of the composition by so-called "low-volume" or"ultra-low volume" methods is also possible.

The composition of the invention can be used also in mixture with eachother active ingredients, for example growth regulants. Plant nutrients,soil-structure improvers, defoliants, plant-protection agents orpesticides, depending on the desired result.

An improvement in the intensity and speed of action can be obtained, forexample, by addition of suitable adjuvants, such as organic solvents,wetting agents and oils. Such additives may allow a decrease in thedose.

The compositions of the invention can suitably be used as powders,dusts, granules, solutions, emulsions or suspensions, with the additionof liquid and/or solid carriers and/or diluents and, optionally,binding, wetting, emulsifying and/or dispersing adjuvants.

Suitable liquid carriers are, for example water, aliphatic and aromatichydrocarbons such as benzene, toluene and xylene, cyclohexanone,isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oilfractions.

Suitable solid carriers include mineral earths, e.g. tonsil, silica gel,talcum, kaolin, attapulgite, limestone, silicic acid and plant products.e.g. flours.

As surface-active agents there can be used for example calciumlignosulphonate. Polyoxyethylenealkylphenyl ether, naphthalenesulphonicacids and their salts, phenolsulphonic acids and their salts,formaldehyde condensates, fatty alcohol sulphates, as well assubstituted benzenesulphonic acids and their salts.

The amount of the mixture (components A and B) in the composition of theinvention in the various preparations can vary over a wide range. Forexample the compostion can contain around 10 to 80 weight percent of themixture, around 90 to 20 weight percent of liquid or solid carriers, aswell as optionally up to 20 weight percent of surfactant.

Formulations can be prepared, for example, from the followingingredients.

(a) 90% mixture (components A+B)

7% kaolin

3% surfactant based on the sodium salt of N-methyl-N-oleyltaurine andcalcium lignosulphonate

(b)

50% mixture (components A+B)

35% colloidal silicic acid

10% calcium lignosulphonate

5% ammonium tetraethyleneglycolnonyl phenyl monosulphate

(c)

30% mixture (components A+B)

2% colloidal silicic acid

6% water

(d)

20% mixture (components A+B)

70% tonsil

8% cell pitch

2% wetting agent based on fatty acid condensation products

(e)

5% mixture (components A+B)

80% tonsilite

10 cell pitch

5% wetting agent based on fatty acid condensation products

The preparation of the composition of the invention can be carried outby mixing the individual components in a suitable apparatus for thispurpose.

The following examples illustrate the possibility of use of thecompositions of the invention.

The examples contain data on components A and B, their rates of use, thepercentage fungicidal acitivity achieved and the percentage inhibitionobtained with the combination of A and B according to the methoddescribed by S. R. Colby, in which the existence of additive activitywould be expected (S. R. Colby "Calculating Synergistic and AntagonisticRespones of Herbicide Combinations" Weeds 15/1 (1967) P 22-22).

The calculation was carried out according to the following equation:##EQU1## in which X=the percentage of fungicidal activity with substanceA at P kg active ingredient/ha

Y=the percentage of fungicidal activity with substance B at g kg activeingredient/ha

E=expected fungicidal activity by A+B at P+q kg/ha.

If the observed value is higher than the value E calculated according toColby, the combination has a synergistic activity.

TEST EXAMPLE

Testing of the composition of the invention against phytophthorainfestans in field tests on potatoes ("Bintje") in test areas of ca. 20m² (four replicates).

Preparations of active ingredients were formulated with water to thedesired concentration using commercially available formulations of theingredients,

The plants were sprayed at a spray interval of 7-12 days with thepreparations of active ingredients. The evaluation was carried out 12days after the last treatment (infestation of the untreated controls was100%).

    ______________________________________                                        Rate of application                                                           (g a · i/ha)                                                                        % Activity                                                     propamocarb                             Trial                                 HCl      maneb     Observed Calculated (E)                                                                            site                                  ______________________________________                                        1125       0       9.5                                                          0      1200      8.7                  I                                     1125     1200      32.5     17.4                                              ______________________________________                                    

In a similar manner the following results were obtained.

    ______________________________________                                        Rate of application                                                           (g a · i/ha)                                                                        % Activity                                                     propamocarb                            Trial                                  HCl      propineb  Observed  Calculated (E)                                                                          site                                   ______________________________________                                        1125       0        9.5                                                         0      1050       1.0                I                                      1125     1050      22.5      10.4                                             ______________________________________                                        propamocarb                            Trial                                  HCl      metiram   Observed  Calculated (E)                                                                          site                                   ______________________________________                                        1125       0        9.5                                                         0      1200       1.2                I                                      1125     1200      28.7      10.6                                             ______________________________________                                        propamocarb                            Trial                                  base     zineb     Observed  Calculated (E)                                                                          site                                   ______________________________________                                        1125       0       67.7                                                         0      2000      77.2                I                                      1125     2000      95.1      92.6                                             1125       0       51.3                                                         0      2000      54.6                II                                     1125     2000      87.4      77.9                                             ______________________________________                                        Rate of application                                                           (g a · i/ha)                                                                        % Activity                                                     propamocarb                                                                            chloro-                       Trial                                  base     thalonil  Observed  Calculated (E)                                                                          site                                   ______________________________________                                        1125       0       67.7                                                         0      1300      82.3                I                                      1125     1300      95.6      94.3                                             1125       0       51.3                                                         0      1300      66.7                II                                     1125     1300      86.2      83.8                                             ______________________________________                                        propamocarb                                                                            copper (I)                    Trial                                  base     oxide     Observed  Calculated (E)                                                                          site                                   ______________________________________                                        1125       0       67.7                                                         0      2250      82.8                I                                      1125     2250      97.0      94.4                                             1125       0       51.3                                                         0      2250      64.4                II                                     1125     2250      91.3      82.7                                             ______________________________________                                    

I claim:
 1. A fungicidal composition comprising a synergisticfungicidally effective amount of the mixture of(a) propyl3-(dimethylamino)propylcarbamate or an acid addition salt thereof, and(b) a compound selected from the group consisting of zincpropylenebis(dithiocarbamate) (propineb). zincethylenebis(dithiocarbamate) (zineb), manganeseethylenebis(dithiocarbamate) (maneb) zinc ammoniateethylenebis(dithiocarbamate)-poly(ethylenethiuramdisulphide) (metiram),and a carrier, wherein the ratio of component A to component B is fromabout 1:01.1 to
 3. 2. The composition according to claim 1, whereincomponent B is propineb, the ratio of component A to component B is fromabout 1:0.5-1.5.
 3. The composition according to claim 1 whereincomponent B is zineb, the ratio of component A to component B is fromabout 1:1.0-3.0.
 4. The composition according to claim 1 whereincomponent B is maneb the ratio of component A to component B is fromabout 1:0.5-1.5.
 5. A composition according to claim 1 wherein componentB is metiram, the ratio of component A to component B is from about1:0.5-1.5.
 6. The composition according to claim 1 wherein component Bis maneb.
 7. A method of combating a fungus which comprises applying tothe fungus or its locus a synergistic fungicidally effective amount of amixture of(a) propyl 3-(dimethylamino)propylcarbamate or an acidaddition salt thereof, and (b) a compound selected from the groupconsisting of zinc propylenebis(dithiocarbamate) polymer (propineb).zinc ethylenebis(dithiocarbamate) polymer (zineb). manganeseethylenebis(dithiocarbamate)-poly(ethylenethiuramdisulphide) zincammoniate (metiram), wherein the ratio of component A to component B isfrom about 1.0.1 to
 3. 8. The method according to claim 7 whereincomponent B is maneb.
 9. The method according to claim 8 wherein theratio of component A to component B is from about 1:0.5 to 1.5.